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Patent 2377898 Summary

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(12) Patent Application: (11) CA 2377898
(54) English Title: FURAN NO-BAKE FOUNDRY BINDERS AND THEIR USE
(54) French Title: LIANTS DE FONDERIE DURCISSANT A FROID ET A BASE DE FURANNE, ET UTILISATION ASSOCIEE
Status: Deemed Abandoned and Beyond the Period of Reinstatement - Pending Response to Notice of Disregarded Communication
Bibliographic Data
(51) International Patent Classification (IPC):
  • B22C 1/22 (2006.01)
(72) Inventors :
  • CHANG, KEN K. (United States of America)
  • HUTCHINGS, DAVID A. (United States of America)
(73) Owners :
  • ASHLAND INC.
(71) Applicants :
  • ASHLAND INC. (United States of America)
(74) Agent: GOWLING WLG (CANADA) LLP
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 2001-04-24
(87) Open to Public Inspection: 2001-11-01
Examination requested: 2002-01-18
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US2001/013207
(87) International Publication Number: WO 2001081024
(85) National Entry: 2001-12-21

(30) Application Priority Data:
Application No. Country/Territory Date
09/559,766 (United States of America) 2000-04-27

Abstracts

English Abstract


This invention relates to furan no-bake foundry binders comprising (a) a
reactive furan resin, (b) furfuryl alcohol, and (c) a catalyst component
comprising a catalytically effective amount of a Lewis acid furan catalyst.
The invention also relates to foundry mixes prepared with the binder, foundry
shapes prepared with the foundry mix, and metal castings prepared with the
foundry shapes.


French Abstract

L'invention concerne des liants de fonderie durcissant à froid et à base de furanne, comprenant: (a) une résine réactive à base de furanne, (b) un alcool furfurylique, ainsi que (c) un composant catalyseur comprenant une dose, efficace sur le plan catalytique, d'un catalyseur à base de furanne et d'acide de Lewis. L'invention concerne également des mélanges de fonderie, préparés à l'aide du liant, des formes de fonderie préparées à l'aide de ce mélange de fonderie, ainsi que des pièces de fonte préparées à l'aide des formes de fonderie.

Claims

Note: Claims are shown in the official language in which they were submitted.


CLAIMS
We claim:
1. A furan no-bake binder comprising:
(a) a reactive furan resin,
(b) furfuryl alcohol, and
(c) a catalyst component comprising a catalytically effective amount of a
Lewis acid furan catalyst.
2. The binder of claim 1 wherein the catalyst component also includes a
conventional
furan catalyst.
3. The binder of claim 2 wherein the weight ratio of active Lewis acid of the
catalyst
component to conventional furan catalyst is from about 1.0: 10 to about 10:1.
4. The binder of claim 3 wherein the reactive furan resin is a mixture of a
conventional furan resin and bis-hydroxymethylfuran resin.
5. The binder of claim 4 that further comprises a polyol.
6. The binder of claim 5 that further comprises an activator selected from the
group
consisting of resorcinol, resorcinol pitch, and bisphenol A tar.
7. The binder of claim 6 that further comprises a bisphenol compound.
8. The binder of claim 7 that also contains a silane.
9. The binder of claim 8 wherein the binder comprises: (a) from about 1 to
about 50
parts by weight a reactive furan resin, (b) from about 10 to about 80 parts by
weight furfuryl alcohol, (c) from about 0.1 to about 20 parts by weight
resorcinol,
(d) from about 1 to about 30 parts by weight a bisphenol, (d) from about 0.1
to
about 30 parts of a polyol, and (f) from about 0.01 to about 10 parts by
weight a
18

silane, wherein said parts of the binder components are by weight are based
upon
100 parts the weight of the binder.
10. The binder of claim 9 wherein the weight ratio of conventional furan resin
to bis-
hydroxymethylfuran resin is from about 1:20 to about 20:1.
11. The binder of claim 10 wherein the polyol is an aromatic polyester polyol
polyester
polyol has a hydroxyl number of about 700 to 1200.
12. The binder of claim 11 wherein the polyester polyol is the reaction
product of an
aromatic polyester selected from the group consisting of phthalic anhydride
and
polyethylene terephthalate and a glycol selected from the group consisting of
ethylene glycol and diethylene glycol.
13. The binder of claim 12 wherein the activator is resorcinol.
14. The binder of claim 13 wherein the bisphenol compound is bisphenol A.
15. The binder of claim 14 wherein the binder comprises: (a) from about 2 to
about 30
parts by weight a reactive furan resin, (b) from about 20 to about 75 parts by
weight furfuryl alcohol, (c) from about 0.5 to about 10 parts by weight
resorcinol,
(d) from about 2 to about 15 parts by weight a bisphenol, (e) from about 2 to
about
20 parts of a polyester polyol, and (f) from about 0.05 to about 5 parts by
weight a
silane, wherein said parts of the binder components are by weight are based
upon
100 parts the weight of the binder.
16. The binder of claim 15 wherein the weight ratio of Lewis acid catalyst to
conventional furan catalyst is from about 1:8 to about 8:1.
17. The binder of claim 16 wherein the Lewis acid catalyst is zinc chloride.
19

18. The binder of claim 17 wherein the conventional furan catalyst is selected
from the
group consisting of sulfonic acid, toluene sulfonic acid, benzene sulfonic
acid, and
mixtures thereof.
19. A foundry mix comprising:
A. a major amount of foundry aggregate; and
B. an effective binding amount of a foundry binder of claims 1, 2, 3, 4, 5, 6,
7,
8, 9, 10, 12, 13, 14, 15, 16, 17, or 18.
20. A process for preparing a foundry shape comprising:
A. shaping the foundry mix of claim 19 into a foundry shape;
B. allowing the foundry shape to harden into a workable foundry shape.
21. A foundry shape prepared in accordance with claim 20.
22. A method for preparing a metal casting comprising:
A. fabricating a shape in accordance with claim 20;
B. pouring said metal while in the liquid state into and around said shape;
C. allowing said metal to cool and solidify; and
D. then separating the molded article.
23. A metal casting prepared in accordance with claim 22.
20

Description

Note: Descriptions are shown in the official language in which they were submitted.


CA 02377898 2001-12-21
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FURAN NO-BAKE FOUNDRY BINDERS AND THEIR USE
FIELD OF THE INVENTION
This invention relates to furan no-bake foundry binders comprising (a) a
reactive
furan resin, (b) furfuryl alcohol, and (c) a catalyst component comprising a
catalytically
effective amount of a Lewis acid furan catalyst. The invention also relates to
foundry
mixes prepared with the binder, foundry shapes prepared with the foundry mix,
and metal
castings prepared with the foundry shapes.
BACKGROUND OF THE INVENTION
One of the most commercially successful no-bake binders is the phenolic-
urethane no-bake binder. This binder provides molds and cores with excellent
strengths that are produced in a highly productive manner. Although this
binder
produces good cores and molds at a high speed, there is an interest in binders
that have
less volatile organic compounds (VOC), free phenol level, free formaldehyde,
and that
produce less odor and smoke during core making and castings. Furan binders
have
these advantages, but their cure speed is much slower than the cure speed of
phenolic
urethane no-bake binders. Furan binders have been modified to increase their
reactivity, for instance by incorporating with urea-formaldehyde resins,
phenol-
2 0 formaldehyde resins, novolac resins, phenolic resole resins, and
resorcinol into the
binder. Nevertheless, these modified furan binders system do not provide the
cure
speed needed in foundries that require high productivity.
U.S. Patent 5,856,375 discloses the use of BPA tar in furan no-bake binders to
increase the cure speed of the furan binder. Although the cure speed of the
binder is
2 5 increased by the addition of the BPA tar, the tensile strength of this
system does not
match that of the phenolic urethane system.
Cure speed is not the only consideration in selecting a binder. Cores and
molds
made with the binder can have unacceptable properties that result in casting
defects
such as veining, penetration, and surface finish, when the cores and molds are
used to
3 0 make metal castings. Veining is an expansion defect that results when a
mold or cores
cracks under thermal stress before the casting solidifies. As a result, molten
metal
enters the cracks of the mold or core and a casting with "veins" or "fins"
results. These
veins or fins must be removed by machining for the casting to be useful.
Mechanical

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penetration occurs when the pressure of molten metal is high enough to force
it into the
interstices of a mold or core surface. The result is an integral mixture of
sand and
metal that is quite difficult to remove in grinding.room operations.
SUMMARY OF THEwINVENTION
This invention relates to furan no-bake binders comprising:
(a) a reactive furan resin,
(b) furfuryl alcohol,
(c) a catalyst component comprising a catalytically effective amount of a
catalyst comprising a Lewis acid.
Preferably the reactive furan resin is mixture of a conventional furan and a
furan derived
from the homopolymerization of binder bis-hydroxymethylfuran. Preferably, the
catalyst
is a mixture of a Lewis acid and a conventional furan catalyst. Preferably,
the binder also
contains an activator selected from the group consisting of resorcinol,
resorcinol pitch, and
bisphenol A tar; a bisphenol compound; a polyol; and a silane.
The binders display several advantages when compared to a conventional furan
no-bake binder. Cores prepared with the binders cure much faster than those
prepared
with conventional furan no-bake binders. In fact, the cure speed of cores
prepared by
the binders of this invention is comparable to that of the phenolic urethane
no-bake
2 0 binder, which is used commercially to make cores where high-speed
production is
needed. The cure speed of cores prepared from this invention is much faster
than those
prepared by the conventional furan no-bake binder that do not use a Lewis acid
as the
catalyst or co-catalyst.
Additionally, the cores made with the binder display excellent tensile
strength
2 5 and excellent casting results. The cores and molds produced by this
invention
exhibited greater resistance to veining than those produced with furan binders
that were
not cured with the Lewis acid catalyst. They also exhibited better resistance
to veining
than cores and molds prepared with phenolic-urethane no-bake binders. The
cores and
molds are produced in a highly productive manner and have good core handling
3 0 strength. The binders are advantageous from an environmental standpoint
because they
contain low VOC, low odor, zero phenol, zero solvent, no isocyanates, and
produce
low smoke when castings are made.
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ENABLING DISCLOSURE AND BEST MODE
The furan resins used in the no-bake binders are preferably low nitrogen furan
resins. The furan resins are conventional furan resins prepared by the
homopolymerization
of furfuryl alcohol (hereafter a conventional furan resin), or preferably
furans prepared by
the homopolymerization of bis-hydroxymethylfuran (hereafter a bis-
hydroxymethylfuran
resin), and mixtures of these resins. These resins are prepared by the
homopolymerization
of the monomer in the presence of heat, according to methods well-known in the
art. The
reaction temperature used in making the furan resins typically ranges from
95°C to 105°C.
1 o The reaction is continued until the percentage of free formaldehyde is
less than 5 weight
percent, typically from 3 to 5 weight percent, and the refractive index is
typically from
1.400 to about 1.500. The viscosity of the resin is preferably from about 200
cps to 450
cps. The furan resins have an average degree of polymerization of 2 to 3.
Although not necessarily preferred, modified furan resins can also be used in
the
binder. Modified furan resins are typically made from furfuryl alcohol, urea
formaldehyde, and formaldehyde at elevated temperatures under slightly
alkaline
conditions at a pH of from 7.0 to 8.0, preferably 7.0 to 7.2. The weight
percent of furfuryl
alcohol used in making the low nitrogen modified furan resins ranges from 60
to 75
percent; the weight percent of the urea formaldehyde used in making the low
nitrogen
2 o modified furan resins ranges from 10 to 25 percent; and the weight percent
of the
formaldehyde used in making the low nitrogen modified furan resins ranges from
1 to 10
percent, where all weight percents are based upon the total weight of the
components used
to make the modified furan resin.
Although not necessarily preferred, urea-formaldehyde resins, phenol-
2 5 formaldehyde resins, novolac resins, and phenolic resole resins may also
be used in
addition to the furan resin.
The furan resin is diluted with furfuryl alcohol to reduce the viscosity of
the
reactive furan resin.
Preferably, an activator is used in the binder. The activator promotes the
3 0 polymerization of furfuryl alcohol and is selected from the group
consisting of resorcinol,
resorcinol pitch, and bisphenol A tar. Preferably used as the activator is
resorcinol.
Resorcinol pitch is defined as the highly viscous product, which remains on
the bottom of
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the reaction vessel after resorcinol is produced and distilled from the
reaction vessel.
Resorcinol pitch is a solid at room temperature and has a melting point of
about 70°C to
80°C. Resorcinol pitch is mostly dimers, trimers, and polymeric
resorcinol. It may also
contain substituted materials. Bisphenol A tar is defined as the highly
viscous product,
which remains on the bottom of the reaction vessel after bisphenol A is
produced and
distilled from the reaction vessel. The bisphenol A tar is a solid at room
temperature and
has a melting point of about 70° C to 80°C. Bisphenol A tar is
mostly dimers, trimers, and
polymeric bis phenol A. It may also contain substituted materials.
Preferably, the binder contains a bisphenol compound. The bisphenol compound
used is bisphenol A, B, F, G, and H, but preferably is bisphenol A.
Preferably, the binder contains a polyol. The polyol is selected from the
group
consisting of polyester polyols, polyether polyols, and mixtures thereof.
Aliphatic
polyester polyols can be used in the binder. Aliphatic polyester polyols are
well known
and are prepared by reacting a dicarboxylic acid or anhydride with a glycol.
They
generally have an average hydroxyl functionality of at least 1.5. Preferably,
the
average molecular weight of the polyester polyol is from 300 to 800. Typical
dicarboxylic acids preferably used to prepare the polyester polyols are adipic
acid,
oxalic acid, and isophthalic acid. The glycols typically used to prepare the
polyester
polyols are ethylene glycol, diethylene glycol and propylene glycol.
2 o The polyether polyols that are used are liquid polyether polyols or blends
of liquid
polyether polyols having a hydroxyl number of from about 200 to about 600,
preferably
about 300 to about 500 milligrams of KOH based upon one gram of polyether
polyol. The
viscosity of the polyether polyol is from 100 to 1,000 centipoise, preferably
from 200 to
700 centipoise, most preferably 300 to 500 centipoise. The polyether polyols
may have
2 5 primary and/or secondary hydroxyl groups.
These polyether polyols are commercially available and their method of
preparation and determining their hydroxyl value is well known. The polyether
polyols
are prepared by reacting an alkylene oxide with a polyhydric alcohol in the
presence of an
appropriate catalyst such as sodium methoxide according to methods well known
in the
3 0 art. Any suitable alkylene oxide or mixtures of alkylene oxides may be
reacted with the
polyhydric alcohol to prepare the polyether polyols. The allcylene oxides used
to prepare
the polyether polyols typically have from two to six carbon atoms.
Representative
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examples include ethylene oxide, propylene oxide, butylene oxide, amylene
oxide, styrene
oxide, or mixtures thereof. The polyhydric alcohols typically used to prepare
the polyether
polyols generally have a functionality greater than 2.0, preferably from 2.5
to 5.0, most
preferably from 2.5 to 4.5. Examples include ethylene glycol, diethylene
glycol, propylene
glycol, trimethylol propane, and glycerine:
Although aliphatic polyester polyols and polyether polyols can be used in the
binder, preferably the polyol used in the polyol component are liquid aromatic
polyester
polyols, or a blend of liquid aromatic polyester polyols, generally having a
hydroxyl
number from about 500 to 2,000, preferably from 700 to 1200, and most
preferably
from 250 to 600; a functionality equal to or greater than 2.0, preferably from
2 to 4; and
a viscosity of 500 to 50,000 centipoise at 25°C, preferably 1,000 to
35,000, and most
preferably 2,000 to 25,000 centipoise. They are typically prepared by the
ester
interchange of an aromatic ester and a polyol in the presence of an acidic
catalyst.
Examples of aromatic esters used to prepare the aromatic polyesters include
phthalic
anhydride and polyethylene terephthalate. Examples of polyols used to prepare
the
aromatic polyesters are ethylene glycol, diethylene glycol, triethylene
glycol, 1,3,
propane diol, 1,4 butane diol, dipropylene glycol, tripropylene glycol,
tetraethylene
glycol, glycerin, and mixtures thereof. Examples of commercial available
aromatic
polyester polyols are STEPANPOL polyols manufactured by Stepan Company,
2 0 TERATE and Phenrez 178 polyol manufactured by Hoechst-Celanese, THANOL
aromatic polyol manufactured by Eastman Chemical, and TEROL polyols
manufactured by Oxide Inc.
It is highly preferred to include a silane in binder. Silanes that can be used
can be
represented by the following structural formula:
R'O
R'O ~SiR
R'O
wherein R' is a hydrocarbon radical and preferably an alkyl radical of 1 to 6
carbon atoms
and R is an alkyl radical, an alkoxy-substituted alkyl radical, or an alkyl-
amine-substituted
3 0 alkyl radical in which the alkyl groups have from 1 to 6 carbon atoms.
Examples of some
commercially available silanes are Dow Corning 26040; Union Carbide A-1100
(gamma
5

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aminopropyltriethoxy silane); Union Carbide A-1120 (N-beta(aminoethyl)-gamma-
amino-
propyltrimethoxy silane); and Union Carbide A-1160 (ureido-silane).
The components are used in the following amounts: (a) from about 1 to about SO
parts by weight a reactive furan resin, preferably about 2 to 30 parts, most
preferably from
6 to 22 parts (b) from about 10 to about 80 parts by weight furfuryl alcohol,
preferably
about 20 to 75, most preferably from 22 to 70, (c) from about 0.1 to about 20
parts by
weight resorcinol, preferably from about 0.5 to 10, most preferably from 0.6
to 8 (d) from
about 1 to about 30 parts by weight a bisphenol, preferably from about 2 tol5,
most
preferably from 3 to 12 (e) from about 0.1 to about 30 parts of a polyester
polyol,
preferably from about 2 to 20, most preferably from 3 to 15, (f) from about
0.01 to about
10 parts by weight a silane, preferably about 0.05 to about 5, most preferably
from 0.07 to
3.
The catalyst component of the furan binder is critical to the effective
practice of
this invention. The catalyst comprises a Lewis acid. Examples of Lewis acids
include
halides of transition metals such as copper chloride, zinc chloride, and
ferric chloride.
Preferably used as the Lewis acid catalyst is zinc chloride. The Lewis acid
catalyst is
typically used in conjunction with another furan curing catalyst. Other furan
curing
catalysts include inorganic or organic acids, preferably organic acids.
Preferably, the
curing catalyst is a strong acid such as toluene sulfonic acid, xylene
sulfonic acid, benzene
2 0 sulfonic acid, HCI, and HZS04. Weak acids such as phosphoric acid can also
be used.
Preferably, a mixture of toluene sulfonic acid/ benzene sulfonic acid is used.
Where
necessary, water is used to compatibilize the Lewis acid with other acid
components.
The amount of curing catalyst used is an amount effective to result in foundry
shapes that
can be handled without breaking. Generally, this amount is from 1 to 45 weight
percent
2 5 active catalyst based upon the weight of total binder, typically from 10
to 40, preferably 15
to 35 weight percent. The weight ratio of Lewis acid in the curing catalyst to
other furan
curing catalyst ranges from about 1:20 to about 20:1 by weight based upon the
total weight
of the active catalyst, preferably about 1:10 to about 10:1, most preferably
from 1:8 to
about 8:1.
3 0 It will be apparent to those skilled in the art that other additives such
as release
agents, solvents, benchlife extenders, silicone compounds, etc. can be used
and may be
added to the binder composition, aggregate, or foundry mix.
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The aggregate used to prepare the foundry mixes is that typically used in the
foundry industry for such purposes or any aggregate that will work for such
purposes.
Generally, the aggregate is sand, which contains at least 70 percent by weight
silica. Other
suitable aggregate materials include zircon, alumina-silicate sand, chromite
sand, and the
like. Generally, the particle size of the aggregate is such that at least 80
percent by weight
of the aggregate has an average particle size between 40 and 1 SO mesh (Tyler
Screen
Mesh).
The amount of binder used is an amount that is effective in producing a
foundry
shape that can be handled or is self supporting after curing. In ordinary sand
type
foundry applications, the amount of binder is generally no greater than about
10% by
weight and frequently within the range of about 0.5% to about 7% by weight
based upon
the weight of the aggregate. Most often, the binder content for ordinary sand
foundry
shapes ranges from about 0.6% to about 5% by weight based upon the weight of
the
aggregate in ordinary sand-type foundry shapes.
Although it is possible to mix the components of the binder with the aggregate
in
various sequences, it is preferred to add the curing acid catalyst to the
aggregate and mix it
with the aggregate before adding the binder.
Generally, curing is accomplished by filling the foundry mix into a pattern
(e.g. a
mold or a core box) to produce a workable foundry shape. A workable foundry
shape is
2 0 one that can be handled without breaking.
Metal castings can be prepared from the workable foundry shapes by methods
well
known in the art. Molten ferrous or non-ferrous metals are poured into or
around the
workable shape. The metal is allowed to cool and solidify, and then the
casting is removed
from the foundry shape.
ABBREVIATIONS
The following abbreviations are used in the Examples:
Bis A bisphenol A
bob based on binder
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bos based on sand
FA furfuryl alcohol
FURAN A furan resin having an average degree of polymerization of about 2 to
3,
prepared by the homopolymerization of furfuryl alcohol under slightly
basic conditions at a reflux temperature of about 100°C
FURAN B furan resin having an average degree of polymerization of about 2 to
3,
prepared by the homopolymerization of bis-hydroxymethylfuran under
acidic conditions at a reflux temperature of about 100°C
pbw parts by weight based upon total parts
PP a polyester polyol prepared by reacting dimethyl terephthalate (DMT)
with diethylene glycol, such that the average molecular weight of the
polyester polyol is about 600
RES resorcinol
RH relative humidity
SIL silane
2 5 ST strip time is the time interval between when the shaping of the mix in
the
pattern is completed and the time and when the shaped mixture can no
longer be effectively removed from the pattern, and is determined by the
Green Hardness tester
TSA/BSA 50:50 blend of toluene sulfonic acid/benzene sulfonic acid (50:50), a
3 0 conventional furan curing catalyst in a solution that contains 32 weight
percent water
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WT work time is the time interval between when mixing begins and when
the mixture can no longer be effectively shaped to fill the mold or core
and is determined by the Green Hardness tester
ZC/SA 80:20 blend of zinc chloride/sulfonic acid, a Lewis acid furan catalyst
within the scope of this invention, where the zinc chloride is 100% solid
and the sulfonic acid is in a solution that contains 32 weight percent
water
EXAMPLES
The examples will illustrate specific embodiments of the invention. These
examples, along with the written description, will enable one skilled in the
art to practice
the invention. It is contemplated that many other embodiments of the invention
will be
operable besides these specifically disclosed.
The foundry binders are used to make foundry cores by the no-bake process
using
a liquid curing catalyst to cure the fi~ran binder. Examples within the scope
of this
invention use a 80:20 blend of ZC/SA. The Comparison Examples use a 50:50
blend of
TSABSA as the curing catalyst. All parts are by weight and all temperatures
are in °C
unless otherwise specified.
2 0 Foundry mixes were prepared by mixing Wedron 540 sand and catalyst for 2
minutes. Then the binders described in the tables were added and mixed for 2
minutes.
The foundry mixes tested had sufficient flowability and produced workable
foundry
shapes under the test conditions.
The resulting foundry mixes were used to fill core boxes to make dogbone
testing
2 5 samples. Test shapes (dogbone shapes) were prepared to evaluate the sand
tensile
development and the effectiveness of the test shapes in making iron castings.
Testing the
tensile strength of the dogbone shapes enables one to predict how the mixture
of sand and
binder will work in actual foundry facilities. The dogbone shapes were stored
at 1 hr, 3 hrs,
and 24 hrs in a constant temperature room at relative humidity of 50% and a
temperature
3 0 of 25 C before measuring their tensile strengths. Unless otherwise
specified, the tensile
strengths were also measured for the dogbone shapes after storing them 24 hrs
at a relative
humidity (RH) of 90 %. Test castings of grey iron, and in some cases, steel,
were made
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with the test cores to predict how the cores would perform when used in
commercial
casting operations.
Example 1 and Comparison A
(Comparison of furan binder cured with ZC/SA and TSA/BSA)
This example compares test castings made with test cores prepared with Binder
A as described below. In one case, the cores were cured ZC/SA (within the
scope of
this invention) and in the other case, the test cores were cured with TSA/BSA
(comparative catalyst). The formulation of Binder A is set forth in Table I.

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Table I
(Example 1 and Comparison A)
Binder A
Component Amount (pbw)
\
FA 52.85
RES 2.71
SIL 0.10
1 o BIS A 7.91
PP 4.44
FURAN A 11.99
Furan B 20.00
In Example l, one weight percent binder (bos) was mixed with 27 weight
percent ZC/SA catalyst (bob). In Comparison A, the binder was mixed with 26%
TSA/BSA catalyst (bob). Binder A is used in both Example 1 and Comparison A.
Cylindrical castings (2" x 2" x 2") were made by pouring molten grey iron
through sand cores made using the curing catalyst of Example 1 and Comparison
A.
2 0 The pouring temperature of the grey iron was 2700°C. The
penetration tests for
veining and mechanical penetration are described by Tordoff and Tenaglia in
AFS
Transactions, pp.149-158 (AFS 84th Annual meeting, St. Louis, Mo., 21-25,
April,
1980). Surface defects were determined by visual observation and rating the
casting
based upon experience. The results are summarized in Table II.
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TABLE II
Grey Iron Casting Results
CATALYST PENETRATION RESISTANCEVEINING RESISTANCE
TSA/BSA
com arative 4.5 4.5
catal st
ZC/SA
catal st of 1.5 2.5
Exam 1e 1
Casting grade: 1= Excellent, 2=Good, 3=Fair, 4=Poor, 5=Very Poor.
The data in Table II indicate that test cores cured with the ZC/SA catalyst
showed increased resistance to veining and penetration during the casting
process when
grey iron was casted. Less veining reduces tooling time, cleaning time, waste,
and
results in increased the productivity in the foundry operation. The erosion
resistance
and surface appearance of the casting prepared with the test core cured with
the
comparative catalyst were similar to that of the casting prepared with the
test core that
was cured with the catalyst of Example 1.
Example 2 and Comparison B
(Comparison of more generic furan binder cured with ZC/SA and TSA/BSA)
This example illustrates the preparation of test cores from a more generic
furan
binder that is cured with the ZC/SA catalyst and TSA/BSA catalyst, and the use
of
2 0 these test cores to cast grey iron. In Example 2, one percent by weight of
binder (bos)
and 27 weight percent of the ZC/SA catalyst (bob) were mixed with Wedron 540
sand.
In Comparison B, 26 weight percent of the TSA/BSA blend (bob) was used instead
of
the ZC/SA catalyst. The binder used in both cases, Binder B, is described in
Table III
below.
Table III
(Formulation for Binder B)
FA 73.57
3 0 PP 16.20
12

CA 02377898 2001-12-21
WO 01/81024 PCT/USO1/13207
FURAN A 10.00
SIL 0.23
Total 100.00
Grey iron castings were prepared in accordance with the procedure set forth in
Example 1. Penetration, veining, and surface finish were evaluated as set
forth in
Example 1. The results are set forth in Table IV.
TABLE IV
Grey Iron Casting Results
CATALYST PENETRATION RESISTANCEVEINING RESISTANCE
TSABSA 4.0 4.0
com arative
catal st
ZC/SA 2.0 3.0
catal st of
Exam 1e 1
The data in Table IV indicate that test cores cured with the ZC/SA catalyst
show increased resistance to veining and penetration during the casting
process using
grey iron. Less veining reduces tooling time, cleaning time, waste, and
results in
increased the productivity in the foundry operation. The erosion resistance
and surface
appearance of the casting prepared with the test core cured with the
comparative
catalyst were similar to that of the casting prepared with the test core that
was cured
2 0 with the catalyst of Example 2.
13

CA 02377898 2001-12-21
WO 01/81024 PCT/USO1/13207
Examples 3 and 4
(Furan binders without bisphenol A and resorcinol)
Test cores were made using 1.2 weight percent (bos) of a binder according to
the procedure of Example 1. The formulations of the binders used are set for
in Table
V that follows. The binder of Example 3 is similar to the binder of Example 1
(Binder
A) except it does not contain bisphenol A or resorcinol. The foundry mixes
used to
prepare the test cores both contained 30 weight percent ZC/SA bob as the
curing
catalyst. The tensile strengths of the test cores were measured and are set
forth in Table
V.
TABLE V
(Furan binders with and without bisphenol A and resorcinol)
Binder Formulations
Example 3 Example 4
FA 73.57 52.85
PP 16.20 4.44
2 0 FURAN 10.00 11.99
SIL 0.23 0.10
Bis A _____ 7.91
~S _____ 2.71
BHF 20.0
2 5 Total 100.0 100.00
14

CA 02377898 2001-12-21
WO 01/81024 PCT/USO1/13207
Table VI
(Tensile Strengths of Test Cores)
Example 3 Example 4
WT/ST (minutes) 13.5/21.3 4.5/6.8
Tensile Strength (psi)
15
minutes 23 36
30 minutes 40 91
1 hour 98 129
24 hour (psi) 335 160
The data in Table VI indicate that, in addition to using the ZC/SA curing
catalyst, it is advantageous to use resorcinol and bisphenol A in the binder,.
Example 5 and Comparison C
2 0 (Comparison of tensile strengths of test cores prepared with a
furan binder and with a phenolic-urethane binder)
Example 5 compares tensile strengths of cores made with the furan binder of
Example 3, but using 25 weight percent 80:20 ZC/TSA (bob) as the curing
catalyst, to
2 5 a phenolic-urethane binder that uses a liquid tertiary amine as the curing
catalyst. The
phenolic-urethane binder is a high-speed commercially available and successful
phenolic-urethane binder system sold as PEPSET~ 2105/2210/3501 system by
Ashland Inc. The test conditions for the phenolic-urethane binder are set
forth below.
The test results are summarized in Table VII.

CA 02377898 2001-12-21
WO 01/81024 PCT/USO1/13207
Test Conditions
Binder: 1.0% based on the sand weight
PEPSET~ binder:
Part I (phenolic resin component)/II (isocyanate component) = 62/38
Catalyst: 3% liquid tertiary amine based on the Part I
TABLE VII
(Tensile Strengths of Test Cores)
to
Example 5 Comparison C
(Binder of Example 3) (PEPSET~ binder)
WT/ST ( minutes) 3.8/6.0 5.0/6.3
Tensile strength
1 hour (psi) 170 162
3 hours (psi) 195 167
2 0 24 hours (psi) 183 259
24 hrs @ 90% RH 73 60
The data in Table VII indicate that the binder of Example 3 using the ZC/SA
curing catalyst has a cure speed comparable to the phenolic-urethane binder.
2 5 Moreover, the test cores made with the binder have comparable tensile
strengths and
their resistance to humidity is much better than the cores prepared with the
phenolic-
urethane binder.
Example 6
3 0 (Casting comparison using grey iron)
Grey iron test castings were made according to the procedure of Example 1
using the binder of Example 3 and the PEP SET~ binder described previously.
The
test conditions were as described in Example 5 and the pouring temperature of
the grey
3 5 iron was 2700 °C. The casting performance is described in, Table
VIII that follows.
TABLE VIII
Grey Iron Casting Results
16

CA 02377898 2001-12-21
WO 01/81024 PCT/USO1/13207
BINDER PENETRATION RESISTANCE VEINING RESISTANCE
PEP SET 1.5 3.5
Exam 1e 6 1.0 1.0
The data in Table VIII indicate that test cores made from a furan binder cured
with the ZC/SA catalyst showed improved resistance to veining for grey iron
castings
when compared to phenolic-urethane system. Less veining reduces tooling time,
cleaning time, waste, and results in increased the productivity in the foundry
operation.
Example 7 and Comparison D
(Casting comparison using steel)
Steel test castings were made according to the procedure of Example 1 using
the
binder of Example 3 and the PEP SET~ binder described previously. The test
conditions were as described in Example 6, and the pouring temperature of the
steel
was 2950° C. The casting performance is described in Table IX that
follows.
TABLE IX
Steel Casting Results
BINDER PENETRATION RESISTANCEVEINING RESISTANCE
PEP SET 1.0 5.0
Exam 1e 1.0 1.0
6
The data in Table IX indicate that test cores made from a furan binder cured
2 o with the ZC/SA catalyst showed improved resistance to veining for steel
castings when
compared to phenolic-urethane system. Less veining reduces tooling time,
cleaning
time, waste, and results in increased the productivity in the foundry
operation.
17

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Event History

Description Date
Application Not Reinstated by Deadline 2005-04-25
Time Limit for Reversal Expired 2005-04-25
Deemed Abandoned - Failure to Respond to Maintenance Fee Notice 2004-04-26
Amendment Received - Voluntary Amendment 2003-09-18
Inactive: IPRP received 2003-07-29
Letter Sent 2003-04-15
Inactive: Single transfer 2003-02-06
Inactive: Cover page published 2002-06-20
Letter Sent 2002-06-18
Inactive: Courtesy letter - Evidence 2002-06-18
Inactive: First IPC assigned 2002-06-16
Inactive: Notice - National entry - No RFE 2002-06-14
Application Received - PCT 2002-04-24
Request for Examination Received 2002-01-18
Request for Examination Requirements Determined Compliant 2002-01-18
All Requirements for Examination Determined Compliant 2002-01-18
National Entry Requirements Determined Compliant 2001-12-21
Application Published (Open to Public Inspection) 2001-11-01

Abandonment History

Abandonment Date Reason Reinstatement Date
2004-04-26

Maintenance Fee

The last payment was received on 2001-12-21

Note : If the full payment has not been received on or before the date indicated, a further fee may be required which may be one of the following

  • the reinstatement fee;
  • the late payment fee; or
  • additional fee to reverse deemed expiry.

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Please refer to the CIPO Patent Fees web page to see all current fee amounts.

Fee History

Fee Type Anniversary Year Due Date Paid Date
MF (application, 2nd anniv.) - standard 02 2003-04-24 2001-12-21
Basic national fee - standard 2001-12-21
Request for examination - standard 2002-01-18
Registration of a document 2003-02-06
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
ASHLAND INC.
Past Owners on Record
DAVID A. HUTCHINGS
KEN K. CHANG
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Claims 2001-12-20 3 90
Abstract 2001-12-20 1 44
Description 2001-12-20 17 657
Notice of National Entry 2002-06-13 1 194
Acknowledgement of Request for Examination 2002-06-17 1 193
Request for evidence or missing transfer 2002-12-23 1 102
Courtesy - Certificate of registration (related document(s)) 2003-04-14 1 107
Courtesy - Abandonment Letter (Maintenance Fee) 2004-06-20 1 175
PCT 2001-12-20 1 51
Correspondence 2002-06-13 1 24
PCT 2001-12-20 1 86
PCT 2001-12-21 5 210